Herbicide composition

ABSTRACT

There is provided an essentially non-aqueous homogeneous liquid herbicide composition comprising: a) a lipophilic solvent soluble complex comprising the reaction product of: i) not in excess of about 35% by weight of one or more lipophobic herbicides having an acidic moiety; and ii) not in excess of about 99% by weight of one or more tertiary dimethylamines of the structure (CH 3 ) 2 N—R wherein R contains an alkyl group of at least 8 carbon atoms and may contain other chemical moieties and wherein is at least one mole equivalent of such amine to each mole of lipophobic herbicide; b) not in excess of about 60% by weight of one or more essentially non-aqueous polar solvents having low volatility; c) not in excess of about 90% by weight of one or more additional solvents selected from the group consisting of low to medium HLB surfactants; and d) not in excess of about 99% by weight of one or more lipophilic carriers.

FIELD OF THE INVENTION

[0001] The invention relates to herbicide compositions. Moreparticularly, the invention relates to essentially non-aqueoushomogeneous herbicide compositions comprising lipophilic solvent solublecomplexes for application without dilution in water.

BACKGROUND OF THE INVENTION

[0002] In this specification, where a document, act or item of knowledgeis referred to or discussed, this reference or discussion is not to betaken as an admission that the document, act or item of knowledge or anycombination thereof was at the priority date:

[0003] (a) part of common general knowledge; or

[0004] (b) known to be relevant to an attempt to solve any problem withwhich this specification is concerned.

[0005] A herbicide composition typically has to be in a form from whichit is available to act upon the target. If, for example, a herbicidecomposition is sprayed on a plant and the carrier evaporates, theherbicide can be left solid and essentially unavailable for uptake.

[0006] Whilst the following discussion concerns glyphosate, it is to beunderstood that the same principles apply to all lipophobic herbicideshaving an acidic moiety.

[0007] Glyphosate is a non-selective herbicide which is applied inaqueous solutions to control weeds in agricultural, industrial anddomestic situations. There has also been development of crops which areresistant to herbicides, such as glyphosate and glufosinate, so that theherbicides may be used post emergent to protect the crop. In thisspecification, the term “glyphosate” refers toN-(phosphonomethyl)glycine CAS No. [1071-83-6]. Currently, glyphosate isneutralised by a base, such as isopropylamine, to allow it to be carriedin an aqueous system.

[0008] Adjuvants are commonly used with these aqueous glyphosatecompositions to improve the efficacy or induce other desirableproperties. Adjuvants can be either formulated into commercialready-to-use glyphosate-containing products or sold as additives to beadded to the tank mix. These adjuvant materials include (i) surfactantsand/or oils for wetting, spreading and spray retention, (ii) bufferingagents and water conditioners for protecting the glyphosate and (iii)polymeric materials which may reduce spray drift.

[0009] Sometimes the adjuvant is lipophilic, such as petroleum oils,vegetable oils or esterified oils, and, in these circumstances, anemulsifying system is also typically necessary to enable the hydrophobicadjuvant to form an emulsion with the aqueous glyphosate composition.When used with lipophilic adjuvants and/or oil carriers, the glyphosateis expected to remain in the aqueous phase and may not fully benefitfrom the use of such a lipophilic adjuvant.

[0010] There have been attempts to improve the efficiency of glyphosatewhich include the use of higher molecular weight amines to form a saltwith the glyphosate. However, most of these attempts with salts ofhigher molecular weight amines were focused on the conventionalglyphosate application system wherein the product is diluted in waterfor use. The amines which are described in these attempts includeprimary, secondary and tertiary amines.

[0011] The authors are aware of only one attempt to form essentiallynon-aqueous compositions of herbicides and these compositions wereintended for application by electrostatic spraying. This attempt teachesthe preferred use of a stoichiometric amount of a primary alkyl aminehaving 13 to 17 carbon atoms to form a salt with the herbicide. It alsoteaches the use of a significant portion of a volatile polar solvent inthe formation of the salt and the composition which is applied.

[0012] Current spray application technology enables the application ofessentially non-aqueous agrochemical compositions as well as aqueouscompositions. Oil-soluble (lipophilic) insecticides and herbicides canbe diluted in lipophilic carriers, such as petroleum or vegetable-basedoils for spraying rather than dilution in water. By choosing appropriatelipophilic carriers, some of the inefficiencies associated with aqueousspray mixtures, such as droplets reflecting off the target, in-flightevaporation and droplet dry-down, can be minimised. Rainfastness of theactive may also be a problem for some products where the activeconstituent may be washed off the target by rain some hours afterapplication but before it has been adequately taken up. Other benefitswhich may be achieved using non-aqueous carriers include enhanced uptakeinto the target and reduced spray volumes.

[0013] Herbicide compositions are also applied using planes orhelicopters. Much of the cost of aerial spraying is associated with theaircraft set up and flying time, hence to be able to spray highlyconcentrated compositions over a larger area without reloading multipletimes allows for more efficient use of aircraft.

[0014] Glyphosate and other lipophobic herbicides, such as glufosinate,are basically insoluble in lipophilic carriers which would allowexploitation of the lower spray volumes. Thus, there has been a need todevelop an essentially non-aqueous carrier system with low volatilityfor a lipophobic herbicide such as glyphosate.

SUMMARY OF THE INVENTION

[0015] It has been found that it is possible to prepare an essentiallynon-aqueous herbicide composition where a lipophobic herbicide, such asglyphosate, is dissolved in a lipophilic carrier using hydrophobictertiary amines to form a lipophilic solvent soluble complex. Thelipophobic herbicide is not dissolved in an aqueous carrier or in anaqueous carrier dispersed in a lipophilic carrier. The essentiallynon-aqueous herbicide composition is then suitable for use withoutdilution in water and may provide a variety of benefits includingreduced spray volumes, improved efficacy and rainfastness.

[0016] In order to minimise inefficiencies such as in-flightevaporation, the choice of the non-aqueous carrier involves the balanceof many factors such as viscosity and volatility. It has further beenfound that the use of tertiary amines with the lipophobic herbicideenables the use of non-volatile polar solvents. This minimises thepossibility that evaporation of the polar solvent will leave thelipophobic herbicide solid on the leaf and essentially unavailable foruptake.

[0017] The herbicide composition according to the invention is suitablefor spraying from all known spraying technology including conventionaltechnology used with aqueous solutions.

[0018] According to a first aspect of the invention, there is providedan essentially non-aqueous homogeneous liquid herbicide compositioncomprising:

[0019] (a) a lipophilic solvent soluble complex comprising the reactionproduct of:

[0020] (i) not in excess of about 35% by weight of one or morelipophobic herbicides having an acidic moiety; and

[0021] (ii) not in excess of about 99% by weight of one or more tertiarydimethylamines of the structure (CH₃)₂N—R wherein R contains an alkylgroup of at least 8 carbon atoms and may contain other chemical moietiesand wherein there is at least one mole equivalent of such amine to eachmole of lipophobic herbicide;

[0022] (b) not in excess of about 60% by weight of one or moreessentially non-aqueous polar solvents having low volatility;

[0023] (c) not in excess of about 90% by weight of one or moreadditional solvents selected from the group consisting of low to mediumHLB surfactants; and

[0024] (d) not in excess of about 99% by weight of one or morelipophilic carriers.

[0025] All proportions are by weight unless otherwise indicated.

[0026] The reaction product (a) may be an isolatable product of thereaction of (i) and (ii) or may be formed in situ.

[0027] The lipophobic herbicide having an acidic moiety has a chemicalstructure which includes one or more acid moieties and is thereforecapable of reacting with a proton acceptor. Where used herein the term“acid” refers to the Bronsted-Lowry definition of an acid. The term“lipophobic herbicide” therefore includes zwitterionic substances.Examples include glyphosate, glufosinate, bilanfos, fosamine or anyother lipophobic herbicide which forms a lipophilic solvent solublecomplex with the tertiary amines.

[0028] The amount of lipophobic herbicide reacted to form the lipophilicsolvent soluble complex is calculated by reference to the free form ofthe lipophobic herbicide as the active ingredient. The amount oflipophobic herbicide in the composition will typically be determined bythe spray rate (litres of spray solution per hectare) and the amount oflipophobic herbicide required to achieve suitable effects. For example,glyphosate is usually sprayed at 250 to 1000 g/ha with a spray rate of50 to 100 L/ha or at ultra low volume rates of 2 to 25 l/ha. Preferably,the amount of lipophobic herbicide is not in excess of 25%. Morepreferably, the amount of lipophobic herbicide is in the range of from0.1 to 10.0% by weight

[0029] When glyphosate is used, the combination of (i) and (ii) may beconsidered by some to be mono-, di- or tri- amine salts of glyphosateand such combinations, however prepared, may be used as the source ofglyphosate in this composition.

[0030] Tertiary amines which are sterically hindered such astributylamine or didecylmethylamine do not form suitably stablecomplexes with the lipophobic herbicides. It has also been found thatthe complexes formed between lipophobic herbicides and amines withconsiderably less steric hindrance such as primary and secondaryalkylamines are difficult to solubilise in lipophilic carriers, prone tocrystallisation in essentially non-aqueous environments and requiresignificant amounts of polar solvent to remain liquid in a lipophiliccarrier. It is thus surprising that the preferred amines for forminglipophilic solvent soluble complexes with lipophobic herbicides such asglyphosate are tertiary dimethylamines.

[0031] The tertiary dimethylamines are of the structure (CH₃)₂N—Rwherein R contains an alkyl group of at least 8 carbon atoms and maycontain other chemical moieties. For example, the tertiarydimethylamines may be selected from dimethylalkylamines or othersubstituted alkyldimethylamines such as alkylamidoalkyldimethylamines.Examples of such tertiary dimethylamines are dimethylcocoamine andoleylamidopropyldimethylamine.

[0032] Provided that there is at least one mole equivalent of tertiarydimethylamines per mole of lipophobic herbicide, it is possible to uselower amines to react with any remaining acidic moieties on thelipophobic herbicide. Excess amine may be used. Preferably, more thanone mole equivalent of tertiary dimethylamine is used per mole ofglyphosate because the lipophilic nature of the complex with thelipophobic herbicide increases such that it becomes even easier todissolve in a chosen lipophilic carrier. The relative amount ofadditional solvent required to aid in solubilising the complex is alsoreduced. Therefore, highly concentrated compositions suited to ultra lowvolume spraying are possible as there is less additional solvent inproportion to the complex in order to dissolve it in a small amount oflipophilic carrier. Preferably, the amount of amine is in the range offrom 1 to 50% by weight. More preferably, the amount of amine is in therange of from 10 to 25% by weight.

[0033] The essentially non-aqueous polar solvents having low volatilitymay be selected from solvents available to those skilled in the art, forexample, butane-1,3-diol, hexylene glycol, 2-ethylhexanol ordipropyleneglycol monomethyl ether. These polar solvents are necessaryfor the formation of the lipophilic complex of the lipophobic herbicidewith the tertiary dimethylamine and subsequent stability of theherbicide composition as a liquid. Typically, the amount of polarsolvent is in the range from equal weight to lipophobic herbicide totwice the lipophobic herbicide weight. In a ready-to-use formulationpreferably the amount of essentially non-aqueous polar solvents whichhave low volatility is in the range of from 1 to 10% by weight.

[0034] Small portions of volatile polar solvents such as water, ethanolor isopropanol may be used to assist the action of the essentiallynon-aqueous polar solvents having low volatility. Such volatiles maylater be readily removed from the composition if desired. Since thesevolatile solvents are used in small proportions the overall stability ofthe composition is not detrimentally effected if the volatile solventevaporates in use.

[0035] The types of reagents which may be used as additional solventsare defined by reference to the term “surfactant”, however, it is notnecessary that these substances exhibit typical surfactantcharacteristics when used in the composition particularly given thatthey are used without dilution in water. All surfactants consist of amolecule that combines both hydrophilic and lipophilic groups. The HLBof a surfactant is an expression of its Hydrophile-Lipophile-Balance,that is, the balance of the size and strength of the hydrophilic andlipophilic groups of the emulsifiers. A surfactant that is predominantlylipophilic is assigned an HLB number in the range 0-10 and a surfactantwhich is predominantly hydrophilic is assigned a higher HLB number above10.

[0036] Examples of suitable surfactants with a low to medium HLB whichmay be used as additional solvents are mono and di-glycerides of fatforming fatty acids (glycerol monooleate or glycerol dioleate), partialfatty acid esters of sorbitol anhydrides (sorbitan monooleate orsorbitan monolaurate), partial fatty acid esters of other polyols suchas pentaerythritol, polyglycerol and sugar pentitols, hexitols and theiranhydrides and lecithin. Further examples include low mole nonionicethoxylates with alkyl or arylalkyl of 12 to 21 carbon atoms and 2 to 9moles ethylene oxide adducted, such as Teric 12A3 (C12 or C12-15 alcoholwith 3 moles ethylene oxide) and Teric DD5 (dodecylphenol with 5 molesethyleneoxide). Still further examples include fatty alkanolamides suchas oleic diethanolamide, organopolysiloxanes or alkylpolyglycosides

[0037] Preferably, there is not in excess of 50% by weight of additionalsolvents. More preferably, the amount of additional solvents is in therange of from 0.4 to 40.0% by weight. The very low levels of theseadditional solvents will be present if commercial spray oil is used asthe lipophilic carrier since adjuvant compositions such as crop oilconcentrates or other self-emulsifying oil-based compositions alreadycontain these surfactants. The amount of additional solvent used fromhalf of the-combined weight of lipophobic herbicide, amine and polarsolvent to about 1.5 times this weight.

[0038] The lipophilic carrier may be any suitable lipophilic carriersknown to those skilled in the art. For example, the lipophilic carriermay be petroleum fractions, vegetable oils, synthetic triglycerides,alkyl esters of fatty acids, fatty alcohols, guerbet alcohols or anymixture thereof. Preferably, the lipophilic carriers are aliphaticparaffinic light distillates or vegetable oils and their derivatives.Typically, a petroleum fraction is used as it has been cost effective.These fractions, for example, can be 70, 100 or 150 second solventneutral. Preferably, there is not in excess of 99% by weight oflipophilic carrier. If the composition is applied to herbicide resistantcrops, then preferably, the lipophilic carrier is low in aromatics.Vegetable oils and their derivatives may be preferred for ecologicalreasons. The choice of the lipophilic carrier may be influenced by itsviscosity and the spray application technology.

[0039] In another embodiment of the invention, the herbicide compositionis a concentrated composition comprising reagents (a) and (b), whichcould itself be sprayed or it could be diluted later with an essentiallynon-aqueous carrier such as reagent (c) and optionally (d). For example,the concentrated composition could be sold in containers of convenientsize and farmers could then dilute the composition with a crop oilconcentrate as desired for the spraying technique to be used. Theinvention includes a concentrate composition comprising additionalsolvents wherein the additional solvents may act as the carrier. Suchcompositions may be sprayed without addition of further solvent or maybe diluted with an essentially non-aqueous lipophilic carrier. Wherelittle or no lipophilic carrier is added then lesser amounts ofadditional solvents are appropriate and facilitate the more concentratedlipophobic herbicide preparations used in ultra low volume spraying.

[0040] The following table sets out the proportions of components whichare typical for essentially non-aqueous glyphosate compositions intendedfor conventional volume, low volume and ultra low volume sprayapplication.

[0041] Similar principles apply to the formation of lipophiliccompositions based on complexes of glufosinate. conventional volume lowvolume spray ultra low volume spray application application sprayapplication 50-100 l/ha 25-50 l/ha 2-25 l/ha Component min typical maxmin typical max min typical max glyphosate 0.1 1 5 0.1 2 10 0.2 5 25 3°amine 0.1 4 25 0.4 8 40 0.8 15 50 polar solvent 0.1 1 10 0.1 2 20 0.2 550 additional solvent 0.1 9 30 1 15 90 2 25 90 lipophilic carrier 50 8599 0 73 98 0 50 95

[0042] In another preferred form of the invention, the herbicidecomposition further comprises one or more pesticides which arecompatible with the lipophilic nature of the herbicide composition. Theterm “pesticides” includes herbicides, fungicides and insecticides. Forexample, 2,4-D may be added to the composition. In some situations,glyphosate, for example, alone is not sufficient to address the farmer'sneeds and a lipophilic herbicide is combined with the glyphosatecomposition.

[0043] In another preferred form of the invention, the herbicidecomposition further comprises one or more other available adjuvantcomponents. The adjuvant component may be selected from plant nutrients,spray drift retardants, stickers, spreaders or viscosity modifiers.

[0044] Non-aqueous solutions of lipophobic herbicides can thus be formedfor spray application in situations where water evaporation or sprayvolume may be an issue.

[0045] According to a second aspect of the invention, there is provideda method for improving rainfastness of a lipophobic herbicide comprisingthe step of formulating the lipophobic herbicide in an essentiallynon-aqueous composition comprising:

[0046] (a) a lipophilic solvent soluble complex comprising the reactionproduct of:

[0047] (i) not in excess of about 35% by weight of one or morelipophobic herbicides having an acidic moiety; and

[0048] (ii) not in excess of about 99% by weight of one or more tertiarydimethylamines of the structure (CH₃)₂N—R wherein R contains an alkylgroup of at least 8 carbon atoms and may contain other chemical moietiesand wherein there is at least one mole equivalent of such amine to eachmole of lipophobic herbicide;

[0049] (b) not in excess of about 60% by weight of one or moreessentially non-aqueous polar solvents having low volatility;

[0050] (c) not in excess of about 90% by weight of one or moreadditional solvents selected from the group consisting of low to mediumHLB surfactants; and

[0051] (d) not in excess of about 99% by weight of one or morelipophilic carriers.

[0052] According to a third aspect of the invention, there is provided amethod for treating weeds comprising the step of applying an essentiallynon-aqueous herbicide composition comprising:

[0053] (a) a lipophilic solvent soluble complex comprising the reactionproduct of:

[0054] (i) not in excess of about 35% by weight of one or morelipophobic herbicides having an acidic moiety; and

[0055] (ii) not in excess of about 99% by weight of one or more tertiarydimethylamines of the structure (CH₃)₂N—R wherein R contains an alkylgroup of at least 8 carbon atoms and may contain other chemical moietiesand wherein there is at least one mole equivalent of such amine to eachmole of lipophobic herbicide;

[0056] (b) not in excess of about 60% by weight of one or moreessentially non-aqueous polar solvents having low volatility;

[0057] (c) not in excess of about 90% by weight of one or moreadditional solvents selected from the group consisting of low to mediumHLB surfactants; and

[0058] (d) not in excess of about 99% by weight of one or morelipophilic carriers.

[0059] According to a fourth aspect of the invention, there is provideda method for preparing an essentially non-aqueous sprayable herbicidecomposition comprising the steps of

[0060] (a) combining the following reagents:

[0061] (i) not in excess of about 35% by weight of one or morelipophobic herbicides having an acidic moiety; and

[0062] (ii) not in excess of about 99% by weight of one or more tertiarydimethylamines of the structure (CH₃)₂N—R wherein R contains an alkylgroup of at least 8 carbon atoms and may contain other chemical moietiesand wherein there is at least one mole equivalent of such amine to eachmole of lipophobic herbicide; and

[0063] (iii) not in excess of about 60% by weight of one or moreessentially non-aqueous polar solvents having low volatility;

[0064] (b) combining the mixture formed in (a) with not in excess ofabout 90% by weight one or more additional solvents selected from thegroup consisting of low to medium HLB surfactants and not in excess ofabout 99% by weight one or more lipophilic carriers.

[0065] Preferably, the reagents in step (a) are combined withheating/stirring. Reflux conditions may be used where appropriate.Preferably, the combining in step (b) comprises stirring the mixturewhilst warm.

[0066] In a further embodiment, the lipophilic solvent soluble complexis prepared and isolated from the essentially non-aqueous polar solventprior to its use. This is useful where the essentially non-aqueous polarsolvent being used is inconvenient as a component of the herbicidecomposition, for example, due to product registration requirements, andit is preferable that it be removed.

[0067] According to a fifth aspect of the invention, there is providedan essentially non-aqueous homogeneous liquid herbicide compositioncomprising:

[0068] (a) a lipophilic solvent soluble complex comprising the reactionproduct of:

[0069] (i) not in excess of about 35% by weight of one or morelipophobic herbicides having an acidic moiety; and

[0070] (ii) not in excess of about 99% by weight of one or more tertiarydimethylamines of the structure (CH₃)₂N—R wherein R contains an alkylgroup of at least 8 carbon atoms and may contain other chemical moietiesand wherein there is at least one mole equivalent of such amine to eachmole of lipophobic herbicide; and

[0071] (b) not in excess of about 60% by weight of one or moreessentially non-aqueous polar solvents which assist the formation of thelipophilic solvent soluble complex, wherein the complex is formed in thepresence of the essentially non-aqueous polar solvent but theessentially non-aqueous polar solvent may be removed after formation ofthe complex if desired.

[0072] According to a sixth aspect of the invention, there is providedan essentially non-aqueous homogeneous liquid herbicide compositioncomprising:

[0073] (a) a lipophilic solvent soluble complex comprising the reactionproduct of:

[0074] (i) not in excess of about 35% by weight of one or morelipophobic herbicides having an acidic moiety; and

[0075] (ii) not in excess of about 99% by weight of one or more tertiarydimethylamines of the structure (CH₃)₂N—R wherein R contains an alkylgroup of at least 8 carbon atoms and may contain other chemical moietiesand wherein there is at least one mole equivalent of such amine to eachmole of lipophobic herbicide;

[0076] (b) not in excess of about 90% by weight of one or moreadditional solvents selected from the group consisting of low to mediumHLB surfactants; and

[0077] (c) not in excess of about 99% by weight of one or morelipophilic carriers.

[0078] It has also been found that it is possible to use a lower amountof tertiary dimethylamines and still obtain an essentially non-aqueoushomogeneous liquid herbicide composition.

[0079] According to a seventh aspect of the invention there is providedan essentially non-aqueous homogeneous liquid herbicide compositioncomprising:

[0080] (a) a lipophilic solvent soluble complex comprising the reactionproduct of:

[0081] (i) not in excess of about 50% by weight of one or morelipophobic herbicides having an acidic moiety; and

[0082] (ii) not in excess of about 99% by weight of one or more tertiarydimethylamines of the structure (CH₃)₂N—R wherein R contains an alkylgroup of at least 8 carbon atoms and may contain other chemicalmoieties, wherein there is less than one mole equivalent of such aminesto each mole of lipophobic herbicide;

[0083] (iii) not in excess of about 20% by weight of one or morehydrophilic amines;

[0084] wherein the total mole equivalents of the amines in (ii) and(iii) is at least equivalent to the moles of lipophobic herbicide;

[0085] (b) not in excess of about 60% by weight of one or moreessentially non-aqueous polar solvents having low volatility;

[0086] (c) not in excess of about 90% by weight of one or moreadditional solvents selected from the group consisting of low to mediumHLB surfactants; and

[0087] (d) not in excess of about 99% by weight of one or morelipophilic carriers.

[0088] Examples of hydrophilic amines include those conventionally usedwith aqueous glyphosate preparations, eg. Isopropylamine, diethanolamineand monoethanolamine.

EXAMPLES

[0089] The invention will now be further illustrated and explained inthe following non-limiting examples.

[0090] The following components were used Ammonium nitrate Ex Orica,Australia (adjuvant component) Break-thru OE 444 Organosilicon exGoldschmidt, USA (additional solvent) BS 1000 Commercial wetting agentex Cropcare, (used in control treatments) Australia 1,3-butanediol ExHoechst Celanese, USA (polar solvent) 2,4-D (herbicide) 2,4-D acid exUnisun, China Diethanolamine Ex Union Carbide (hydrophilic amine)Dimethylcocoamine Ex Proctor & Gamble, USA (tertiary dimethylamine)Esterol 123 Ethyl oleate (80% ethyl/20% methyl) ex (lipophilic solvent)Victorian Chemical Company, Australia Esterol 272 Glyceryl mono-oleateex Victorian (additional solvent) Chemical Company, Australia EthanolAnhydrous, 100SGF3 grade methanol (volatile solvent) denatured ex CSR,Australia Glufosinate 3-amino-3-(carboxypropyl)methyl- (lipophobicherbicide) phosphonic acid ex Aventis, GlyphosateN-(phosphonomethyl)glycine (98% (lipophobic herbicide) minimum) exDavison Industries, Australia or Unisun Chemicals, China Glysolv DPMDipropyleneglycol monomethyl ether ex (polar solvent) Huntsman,Australia Hexylene glycol Ex Tiger Chemicals, Australia (polar solvent)Iso-octanol Ex Bentley-Chemplax, Australia (polar solvent)Monoethanolamine Ex Union Carbide (hydrophilic amine)Oleylamidopropyldimethylamine Prepared by reaction of oleic acid with(tertiary dimethylamine) N,N-dimethylaminopropylamine at VictorianChemical Company, Australia Phosphoric acid 81% aqueous Ex DeltrexChemicals, Australia Prorex 36 100 solvent neutral mineral oil Ex(lipophilic carrier) Mobil, Australia Shell P878 300 test kerosene exShell, Australia (lipophilic carrier) Span 80 Sorbitan mono-oleate exHuntsman (additional solvent) Corporation, Australia Teric 12A3 C12-15synthetic alcohols and 3 moles (additional solvent) ethylene oxide exHuntsman Corporation, Australia Teric DD5 dodecylphenol and 5 molesethylene (additional solvent) oxide ex Huntsman Corporation, AustraliaTerwet 3001 Alkyl polyglucoside ex Huntsman, (additional solvent)Australia Vicamid 825 Oleyldiethanolamide ex Victorian (additionalsolvent) Chemical Company, Australia VOC RHT 70 70 solvent neutralmineral oil ex (lipophilic carrier) Safety-Kleen, USA

Example 1

[0091] 62.5 parts dimethylcocoamine, 15 parts glyphosate, 15 parts1,3-butanediol and 7.5 parts ethanol were refluxed together for 15minutes to form a single phase liquid with about 15% of glyphosatepresent.

[0092] This formulae is useful when high glyphosate content is required.For example, this formula is appropriate for use in ultra low volumecrop spraying.

Example 2

[0093] The following compositions were prepared and resulted in clearliquids containing about 7.5% glyphosate. The dimetbylcocoamine, ethanoland glyphosate were refluxed together to form a single phase liquid. Theadditional solvent was then added and mixing continued at 40 to 70° C.These compositions may be used for ultra low volume spray applicationdirectly. They are also soluble in VOC RHT 70 and therefore can beconverted to compositions suitable for low volume spray application.However, loss of ethanol from these formulations resulted in unstablecompositions. Composition 1 2 3 Dimethylcocoamine 33 33 33 Ethanol 9 9 9Glyphosate 7.5 7.5 7.5 Span 80 — — 50.5 Teric DD5 — 50.5 — Teric 12A350.5 — —

Example 3

[0094] 32 parts dimethylcocoamine, 8 parts 1,3-butanediol and 8 partsglyphosate were mixed together at 60° C. for one hour. 24 parts Span 80,2 parts Glysolv DPM and 26 parts Esterol 272 were then added and mixingcontinued at 40 to 70° C. until a clear liquid was formed with about 8%glyphosate acid.

[0095] This composition is soluble in VOC RHT 70 if a more dilutecomposition is desired.

[0096] Use of 1,3-butanediol rather than ethanol minimised the vapourloss during formation of the composition.

Example 4

[0097] 2 parts glyphosate was combined with 8 parts dimethylcocoamineand 4 parts ethanol and refluxed with stirring until clear to formMixture A. When cooled, Mixture A was a liquid paste with about 14-15%glyphosate.

[0098] 20 parts of Esterol 272 was added to Mixture A and warmed at 30to 50° C. with stirring until clear to form Mixture B. When cooled,Mixture B was a clear viscous liquid with about 5-6% glyphosate.

[0099] 34 parts of Mixture B was combined with 66 parts of VOC RHT 70 toprovide a clear liquid with 2% glyphosate.

[0100] If 340 parts of Mixture B is diluted to 1 litre with VOC RHT 70,a preparation containing 2% w/v suitable for spraying is obtained.

[0101] If 340 parts of Mixture B is diluted to 4 litres with VOC RHT 70,a preparation containing 0.5% w/v suitable for spraying is obtained.

Example 5

[0102] 79 parts of dimethylcocoamine was combined with 21 parts ofglyphosate and 40 parts ethanol and refluxed until a clear solution wasformed. 210 parts of Esterol 272, 15 parts of Break-thru OE 444 and 635parts of VOC RHT 70 were added with mixing at 30 to 50° C. The finalproduct was a clear liquid with about 2% glyphosate present.

Example 6

[0103] 90 parts of dimethylcocoamine was combined with 20 partsglyphosate and 30 parts ethanol and refluxed until a clear solution wasformed. 195,parts of Esterol 272, 15 parts Teric DDS (or Teric 12A3) and650 parts VOC RHT 70 were then added with mixing at 30 to 50° C. Thefinal product was 1000 parts of a clear liquid with about 2% glyphosatepresent.

[0104] This formulation enables farmers and/or aerial operators to useself-emulsifying mineral oil compositions that contain surfactants, suchas crop oil concentrates, as the lipophilic carrier when preparing thecomposition.

Example 7

[0105] Glyphosate (50 parts), 1,3-butanediol (50 parts), ethanol (50parts) and dimethylcocoamine (132 parts, approximately 2.14 molarequivalent to glyphosate) were refluxed at 80-90° C. with stirring for90 minutes until clear to form Mixture C. Mixture C was a clear liquidwith 17-18% glyphosate.

[0106] Mixture C (20 parts) was combined with Esterol 272 (30 parts) toprovide a clear liquid with 7% glyphosate.

[0107] Mixture C (24g) was combined with Esterol 272 (36 g) and asufficient amount of Shell P878 to provide 200 ml of a clear liquid with2% w/v glyphosate.

Example 8

[0108] Glyphosate (50 parts), 1,3-butanediol (50 parts), ethanol (50parts), dimethylcocoamine (71 parts, approximately 1.07 molar equivalentto glyphosate) and water (20 parts) were refluxed at 80-90° C. withstirring for one hour. Esterol 272 (118 parts), Vicamid 825 (66 parts)and Span 80 (57 parts) were then added and the mixture warmed withstirring to form Mixture D, a clear liquid with 10-11% glyphosate.

[0109] Mixture D (40g) was combined with a sufficient amount of ShellP878 to form 200 ml of a clear liquid with 2% w/v glyphosate.

Example 9

[0110] In this example, compositions containing different lipophobicherbicides were tested. The amount of herbicide per hectare was loweredto below the typical application rate to enable an assessment of thedifference effectiveness of the compositions.

[0111] The inclusion of non-volatile polar solvents was consideredessential for these and subsequent formulations following instabilityproblems noted with earlier compositions upon loss of ethanol.

[0112] The following compositions were tested. Lipophobic herbicidesDimethylcocoamine Polar solvent Additional solvent Lipophilic carrierComposition (g/L) (g/L) (g/L) (g/L) (to 1 litre) 4. Glyphosate 2.59 3.691,3- 2.59 Esterol 31.1 VOC RHT 70 (25 g/ha) butanediol 272 Ethanol 2.59Span 80 2.95 Water 1.04 Vicamid 3.42 825 5. Glyphosate 7.68 10.91 1,3-7.68 Esterol 64.07 VOC RHT 70 (75 g/ha) butanediol 272 Ethanol 7.68 Span80 8.75 Water 3.06 Vicamid 10.14 825 6. Glyphosate 15.36 21.82 1,3-15.36 Esterol 68.14 VOC RHT 70 (150 g/ha) butanediol 272 Ethanol 15.36Span 80 17.5 Water 6.12 Vicamid 20.28 825 7. Glyphosate 2.57 7.29 1,32.57 Esterol 30 VOC RHT 70 (25 g/ha) butanediol 272 Ethanol 2.57 8.Glyphosate 7.71 21.87 1,3 7.71 Esterol 50 VOC RHT 70 (75 g/ha)butanediol 272 Ethanol 7.71 9. Glyphosate 15.42 43.74 1,3 15.42 Esterol60 VOC RHT 70 (150 g/ha) butanediol 272 Ethanol 15.42 10. Glyphosate2.57 10.26 1,3 2.97 Vicamid 60 VOC RHT 70 (25 g/ha) butanediol 825 Water50 Teric 65 12A3 11. Glyphosate 7.71 30.87 1,3 8.92 Vicamid 80 VOC RHT70 (75 g/ha) butanediol 825 Water 50 Teric 65 12. Glyphosate 2.57 10.261,3 2.97 Esterol 24.2 Esterol 123 (25 g/ha) butanediol 272 13.Glyphosate 7.71 30.87 1,3 8.92 Esterol 52.5 Esterol 123 (75 g/ha)butanediol 272 14. Glyphosate 15.42 61.73 1,3 17.85 Esterol 65 Esterol123 (150 g/ha) butanediol 272 15. Glyphosate 2.57 10.26 1,3 2.97 Esterol34.2 VOC RHT 70 (25 g/ha) butanediol 272 16. Glyphosate 7.71 30.87 1,38.92 Esterol 52.5 VOC RHT 70 (75 g/ha) butanediol 272 17. Glyphosate15.42 61.73 1,3 17.85 Esterol 80 VOC RHT 70 (150 g/ha) butanediol 27218. Glufosinate 5 30 1,3 15 Esterol 124 VOC RHT 70 (50 g/ha) butanediol272 19. Glufosinate 20 120 1,3 60 Esterol 183 VOC RHT 70 (200 g/ha)butanediol 272 20. Glyphosate 7.5 37.5 1,3 11.25 Esterol 86.25 VOC RHT70 (75 g/ha) butanediol 272 2,4-D 7.52 (75 g/ha) 21. Glyphosate 15 751,3 22.50 Esterol 122.5 VOC RHT 70 (150 g/ha) butanediol 272 2,4-D 15(150 g/ha) 22. Glyphosate 7.5 45 1,3 20 Esterol 90 VOC RHT 70 (75 g/ha)butanediol 272 2,4-D 15 (150 g/ha)

[0113] The following control treatments were used. Glyphosate refers toGlyphosate CT (containing 450 g/l glyphosate as the isopropylaminesalt), 2,4-D refers to Amicide 500 (containing 2,4-D 500 g/l as thedimethylamine salt) and Glufosinate refers to BASTA (containingglufosinate-ammonium 200 g/l). Control 7 assesses the damage caused bythe lipophilic composition with citric acid substituted for theherbicide. Control 1 25 g/ha glyphosate in aqueous solution with 0.1% BS1000 Control 2 75 g/ha glyphosate in aqueous solution with 0.1% BS 1000Control 3 150 g/ha glyphosate in aqueous solution with 0.1% BS 1000Control 4 VOC RHT 70 Control 5 Esterol 123 Control 6 Glyphosate (75g/ha), 2,4-D (150 g/ha) in aqueous solution with 0.1% BS 1000 Control 720 g/L citric acid, 20 g/L 1,3-butanediol, 70 g/L dimethyl- cocoamine,100 g/L Esterol 272 and VOC RHT 70 to 1 litre. Control 8 Glyphosate (75g/ha), 2,4-D (75 g/ha) in aqueous solution with 0.1% BS 1000 Control 9Glyphosate (150 g/ha), 2,4-D (150 g/ha) in aqueous solution with 0.1% BS1000 Control 10 Glufosinate (50 g/ha) Control 11 Glufosinate (200 g/ha)Control 12 2,4-D (150 g/ha)

[0114] Method

[0115] The treatments were applied to Ryegrass and/or Spiny Emex in bothstandard conditions and with simulated 10 mm rain two hours afterspraying. Each test had 7 replicates. The plants were assessed 14 daysafter spraying.

[0116] The control treatments containing herbicides were diluted inwater and applied at a rate of 64 l/Ha. The test essentially non-aqueouscompositions were applied directly at a rate of 10 l/Ha.

[0117] Results

[0118] A hyphen (-) means that the composition was tested in thosecircumstances. Fresh weight (g/plant) Ryegrass Ryegrass Spiny Emex SpinyEmex Treatment with no rain with rain with no rain with rain Notreatment 2.07  2.07  10.4  10.44 Control 1 1.162 1.564 - - Control 20.308 1.192 8.32 10.37 Control 3 0.236  0.5000 6.04  9.02 Control 41.142 - 11.6  - Control 5 1.443 - - - Control 6 0.417 1.198 5.53  9.91Control 7 1.50  - 12.3  - Control 8 - - 6.93 10.19 Control 9 - - 5.71 8.55 Control 10 - - 8.59 11.05 Control 11 - - 1.26 10.07 Control 12 - -9.27  7.52 Composition 4. 0.895 - - - Composition 5. 0.183 - - -Composition 6. 0.117 - - - Composition 7. 0.339 - - - Composition 8.0.261 - - - Composition 9. 0.106 - - - Composition 10. 0.311 - - -Composition 11. 0.292 - - - Composition 12. 0.338 0.682 - - Composition13. 0.124 0.254 - - Composition 14. 0.133 0.224 - - Composition 15.0.390 0.614 - - Composition 16. 0.117 0.197 5.13  4.56 Composition 17.0.104 0.321 2.11  2.95 Composition 18. - - 4.78  7.37 Composition19. - - 3.71  4.44 Composition 20. - - 4.16  4.58 Composition 21. - -3.42  3.26 Composition 22.  0.1543 0.978 4.08  6.59

[0119] LSD (P=0.05) 0.300

[0120] Conclusions

[0121] (a) Glyphosate

[0122] At the three concentration levels of 25, 75 and 150 g/Ha, thetest compositions performed better than the control treatments onRyegrass with no rain. In rain conditions, the test compositions 12 to17 performed significantly better than the control treatments and indeedare comparable with or outperform the control treatments 1-3 withoutrain.

[0123] Compositions 10 and 11 which contained water did not provideimproved results over those without water.

[0124] On Spiny Emex, at the concentration levels of 75 and 150 g/Ha,test compositions 16 and 17 performed markedly better than the controltreatments 2-3 in both no rain and rain conditions. The controltreatments were not effective to control Spiny Emex in rain conditions,however test compositions 16 and 17 in rain conditions outperformed thecontrol treatments without rain.

[0125] Therefore, the compositions of the invention providedrainfastness for the herbicide.

[0126] (b) Glyphosate and 2,4-D

[0127] Composition 22 on Ryegrass performed better than Control 6 bothwith rain and without rain.

[0128] On Spiny Emex, Compositions 20 to 22 performed better thanControls 6, 8 and 9. Again, the control treatments were not effective tocontrol Spiny Emex in rain conditions, but the compositions of theinvention in the rain were comparable or outperformed with the controltreatments without rain indicating that the composition of the inventionprovided rainfastness for the herbicide.

[0129] (c) Glufosinate

[0130] Without rain on Spiny Emex, Composition 18 performed better thanControl 10 therefore the composition of the invention provides anadjuvant effect at a concentration of 50 g/Ha of glufosinate.

[0131] In rain, Compositions 18 and 19 performed better than Controls 10and 11 which were not effective at controlling Spiny Emex. Therefore,the compositions of the invention provided rainfastness for theherbicide.

Example 10

[0132] In this example, essentially non-aqueous compositions containingglyphosate were tested for efficacy.

[0133] The following compositions were tested. GlyohosateDimethylcocoamine Polar solvent Additional solvent Lipophilic carrierComposition (g/L) (g/L) (g/L) (g/L) (to 1 litre) 23. 21 79.1 1,3 24Breakthru OE 16 VOC RHT 70 butanediol 444 Glysolv DPM 9 Esterol 272 47Span 80 46.5 24. 5.25 19.8 1,3 6 Breakthru OE 16 VOC RHT 70 butanediol444 Glysolv DPM 2 Esterol 272 21.5 Span 80 11.5 25. 2.1 7.91 1,3 2.4Breakthru OE 16 VOC RHT 70 butanediol 444 Glysolv DPM 1 Esterol 272 12.5Span 80 5 26. 21 90 1,3 24 Esterol 272 10 VOC RHT 70 butanediol Teric12A3 60 Teric DD5 30 27. 5.25 22.5 1,3 6 Esterol 272 10 VOC RHT 70butanediol Span 80 5 Teric 12A3 15 Teric DD5 7.5 28. 2.1 9 1,3 2.4Esterol 272 5 VOC RHT 70 butanediol Span 80 7.5 Teric 12A3 10 Teric DD55 29. 21.1 84.4 1,3 24.5 Esterol 272 43.3 Shell P878 butanediol GlysolvDPM 9.3 Span 80 43.3 30. 5.3 21.1 1,3 6.1 Esterol 272 19 Shell P878butanediol Glysolv DPM 2 Span 80 14 31. 2.11 8.44 1,3 2.45 Esterol 27212.5 Shell P878 butanediol Glysolv DPM 1 Span 80 10 32. 21.1 84.4 1,324.5 Teric 12A3 45 Shell P878 butanediol Water 50 Teric DD5 10 (AmmoniumTerwet 3001 22.5 nitrate 20) Vicamid 825 50 33. 5.3 21.1 1,3 6.1 Teric12A3 45 Shell P878 butanediol Water 50 Teric DD5 10 (Ammonium Terwet3001 22.5 nitrate 20) Vicamid 825 50 34. 2.11 8.44 1,3 2.45 Teric 12A345 Shell P878 butanediol Water 50 Teric DD5 10 (Ammonium Terwet 300122.5 nitrate 20) Vicamid 825 50

[0134] The following control treatments were used. Control 1  50 g/haglyphosate in aqueous solution with 0.1% BS 1000 Control 2 125 g/haglyphosate in aqueous solution with 0.1% BS 1000 Control 3 500 g/haglyphosate in aqueous solution with 0.1% BS 1000

[0135] Method

[0136] The treatments were applied to ryegrass in conditions equivalentto no rain and 10 mm rain two hours after spraying. Each test had 7replicates. The plants were assessed 14 days after spraying.

[0137] The control treatments containing herbicides were applied at arate of 64 l/Ha according to current practice.

[0138] The test essentially non-aqueous compositions were too viscousfor spraying and were diluted 1:1 with Shell P878 and sprayed at 50l/ha.

[0139] Results Fresh weight (g/plant) Ryegrass Ryegrass Treatment withno rain with rain No treatment 1.862 1.862 Control 1 0.969 1.268 Control2 0.281 0.663 Control 3 0.234 0.309 Blank oil 1.093 — Composition 23.0.217 0.181 Composition 24. 0.286 0.211 Composition 25. 0.381 0.389Composition 26. 0.194 0.203 Composition 27. 0.284 0.292 Composition 28.0.362 0.411 Composition 29. 0.260 0.218 Composition 30. 0.404 0.322Composition 31. 0.323 0.748 Composition 32. 0.481 0.385 Composition 33.0.281 0.208 Composition 34. 0.375 0.313

[0140] LSD (P=0.05) 0.191

[0141] Conclusions

[0142] The test results show that glyphosate is active in a non-aqueousenvironment with comparable or better results.

[0143] Rainfall after application is known to reduce the efficacy ofcertain products including glyphosate-based herbicides. This isevidenced by comparing the results for the commercial products with andwithout simulated rainfall as shown in the above Table where the FreshWeight for each of the Controls 1, 2 and 3 is higher for each examplewhere rain is applied. By contrast, the non-aqueous Compositions 23 to30 do not show such loss of activity when simulated rainfall was appliedand can be said to be rainfast.

Example 11

[0144] In this example, essentially non-aqueous compositions containingglyphosate were tested for efficacy.

[0145] The following compositions were tested. In the table thefollowing abbreviations are used: DMC Dimethylcocoamine (tertiary) OAPAOleylamidopropyldimethylamine (tertiary) DEA Diethanolamine(hydrophilic) MEA Monoethanolamine (hydrophilic)

[0146] Polar Additional Lipophilic carrier Composition Glyphosate (g)Amine (g) solvent (g) solvent (g) (to 2 litre) 35. 10.2 DMC 271,3-butanediol 10 Esterol 272 60 VOC RHT 70 hexylene glycol 12 36. 10.2DMC 14 1,3-butanediol 4 Esterol 272 35 VOC RHT 70 2-ethylhexanol 4 DEA0.6 Ethanol 2 Vicamid 825 35 water 3 37. 10.2 OAPA 31 1,3-butanediol 5Esterol 272 76 VOC RHT 70 Water 5 Glysolv DPM 7.5 38. 10.2 OAPA 451,3-butanediol 5 Vicamid 825 15 VOC RHT 70 water 5 Esterol 272 100 39.10.2 OAPA 2.8 1,3-butanediol 5.6 Vicamid 825 30 Prorex 36 MEA 4 water7.5 Esterol 272 32.8 3 and VOC RHT 70 40. 10.2 DMC 2 1,3-butanediol 5.6Vicamid 825 25 Prorex 36 MEA 4 water 7.5 Esterol 272 29 3 and VOC RHT 70

[0147] Composition 35 to 40 each have 0.5% w/v glyphosate. Thesetreatments were sprayed at 50 l/ha to give 50g/ha of glyphosate understandard conditions and with 5 mm simulated rain 2 hours afterapplication. Control 2 was sprayed in equivalent amounts.

[0148] The above compositions are being tested against the followingcontrol treatment. Control 1 Roundup Max (glyphosate 510 g/l as the MBAsalt) diluted in water and sprayed at 64 l/ha top give 50 and 150 g/haof glyphosate. Control 2 50 g water, 30 g citric acid, 30 g1,3-butanediol, 30 g hexylene glycol, 90 g Vicamid 825 , 70 gOleylamidopropyl- dimethylamine, 210 g Esterol 272 VOC RHT 70 to 2 L.

[0149] Results

[0150] Each test had seven replicates and the plants were assessed 14days after spraying. Fresh weight (g) Treatment Standard conditions 5 mmrain No treatment 3.42 Control 1 (50 g/ha) 1.07 2.88 Control 1 (150g/ha) 0.74 1.40 Control 2 2.49 3.37 Composition 35. 1.47 1.85Composition 36. 1.61 1.42 Composition 37. 1.16 1.78 Composition 38. 0.761.06 Composition 39. 0.89 2.60 Composition 40. 1.48 3.75

[0151] LSD (P=0.05) 0.78

[0152] Conclusion

[0153] Examples 35 to 38 all contain at least one mole equivalent oftertiary dimethylamine to each mole of glyphosate. Examples 39 and 40contain less than one (approx 0.16 mole equivalent for each) moleequivalent of tertiary dimethylamine to each mole of glyphosate with theremainder of the glyphosate being complexed with the hydrophilic aminemonoethanolamine in accordance with the sixth aspect of the invention.

[0154] Each of the examples 35 to 40 show similar efficacy to thecommercial product Round-Up Max under the Standard Conditions.

[0155] Examples 35 to 38 are less affected by simulated rainfall thanexamples 39 and 40 or the Control 1. The increase in fresh weight is upto 50% for examples 35 to 38 (reduction seen for 36) whilst for each ofExamples 39, 40 and Control 1, the increase in fresh weight is greaterthan 100%. Examples 35 to 38 or compositions containing at least onemole equivalent of tertiary dimethylamine to each mole of glyphosate aremore rainfast than other lipophilic compositions or the aqueous control.

Example 12

[0156] Most of the compositions shown in the previous examples have beendesigned to be tested at sublethal doses of the herbicide forcomparative testing, or are suitable as herbicidal compositions whensprayed at rates considerably greater than 10 l/ha.

[0157] The following Compositions 41 to 46 have been prepared asexamples of essentially non-aqueous herbicide compositions eachcontaining 50 g/l of the herbicide glyphosate. These examples areconsidered to be suitable herbicidal compositions for spraying at 10l/ha to provide 500 g/ha of the active.

[0158] In the table the following abbreviations are used: DMCDimethylcocoamine (tertiary) OAPA Oleylamidopropyldimethylamine(tertiary) DEA Diethanolamine (hydrophilic) MEA Monoethanolamine(hydrophilic)

[0159] Glyphosate Amine Polar solvent Additional solvent Lipophiliccarrier Composition (g) (g) (g) (g) (to 100 ml) 41. 5.1 DMC 13.5 1,3- 5Esterol 272 12.5 VOC RHT 70 butanediol hexylene 5 glycol 42. 5.1 DMC13.5 1,3- 5 Esterol 272 12.5 VOC RHT 70 butanediol hexylene 5 Breakthru0.6 glycol OE444 43. 5.1 DMC 7 1,3- 2 Esterol 272 12 VOC RHT 70butanediol DEA 0.3 2- 2 Vicamid 825 13 ethylhexanol 44. 5.1 DMC 1.0 1,3-2.8 Vicamid 825 8 VOC RHT 70 butanediol DEA 2.0 water 3.7 Esterol 272 945. 5.1 OAPA 22.7 1,3- 3.6 Esterol 272 21.6 VOC RHT 70 butanediolGlysolv DPM 5.4 46. 5.1 OAPA 22.7 1,3- 3.6 Esterol 272 21.6 Esterol 123butanediol Glysolve DPM 5.4

Example 13

[0160] In this example, a composition containing glyphosate and 2,4-Dwas prepared. Glyphosate  51 parts 2,4-D octyl ester  38 parts Water  2parts 1,3-butanediol  20 parts Dimethylcocamine 121 parts

[0161] The final composition contained 19.9% w/v glyphosate. This was aconcentrated composition suitable for sale to farmers who may thenfurther dilute the composition with additional solvents and lipophiliccarriers or with a crop oil concentrate.

[0162] The word ‘comprising’ and forms of the word ‘comprising’ as usedin this description does not limit the invention claimed to exclude anyvariants or additions.

[0163] Modifications and improvements to the invention will be readilyapparent to those skilled in the art. Such modifications andimprovements are intended to be within the scope of this invention.

What is claimed is:
 1. An essentially non-aqueous homogeneous liquidherbicide composition comprising: (a) a lipophilic solvent solublecomplex comprising the reaction product of: (i) not in excess of about35% by weight of one or more lipophobic herbicides having an acidicmoiety; and (ii) not in excess of about 99% by weight of one or moretertiary dimethylamines of the structure (CH₃)₂N—R wherein R contains analkyl group of at least 8 carbon atoms and may contain other chemicalmoieties and wherein there is at least one mole equivalent of such amineto each mole of lipophobic herbicide; (b) not in excess of about 60% byweight of one or more essentially non-aqueous polar solvents having lowvolatility; (c) not in excess of about 90% by weight of one or moreadditional solvents selected from the group consisting of low to mediumHLB surfactants; and (d) not in excess of about 99% by weight of one ormore lipophilic carriers.
 2. A composition according to claim I whereinthe lipophobic herbicide is selected from the group comprisingglyphosate, glufosinate, bilanfos, fosamine or mixtures thereof.
 3. Acomposition according to claim 2 wherein the lipophobic herbicide isglyphosate.
 4. A composition according to claim 2 wherein the lipophobicherbicide is glufosinate.
 5. A composition according to claim 1 whereinthe amount of lipophobic herbicide is not in excess of 25% by weight. 6.A composition according to claim 1 wherein the amount of lipophobicherbicide is in the range of from 0.1 to 10% by weight.
 7. A compositionaccording to claim 1 wherein the tertiary dimethylamines are selectedfrom the group consisting of dimethylalkylamines,alkylamidoalkyldimethylamines, other substituted dimethylalkylamines andmixtures thereof.
 8. A composition according to claim I wherein theamount of tertiary dimethylamines used is in the range of from 1 to 50%by weight.
 9. A composition according to claim I wherein the amount oftertiary dimethylamines used is in the range of from 10 to 25% byweight.
 10. A composition according to claim 1 wherein the essentiallynon-aqueous polar solvents having low volatility are selected from groupconsisting of butane-1,3-diol, hexylene glycol or dipropyleneglycolmonomethyl ether.
 11. A composition according to claim 1 wherein theamount of essentially non-aqueous polar solvent having low volatility isin the range of from 0.2 to 5% by weight.
 12. A composition according toclaim 1 wherein the additional solvent is selected from the groupconsisting of mono and di-glycerides of fat forming fatty acids,glycerol monooleate, glycerol dioleate, partial fatty acid esters ofsorbitol anhydrides, sorbitan monooleate, sorbitan monolaurate, partialfatty acid esters of other polyols, pentaerythritol, polyglycerol, sugarpentitols and their anhydrides, sugar hexitols and their anhydrides,lecithin, low mole nonionic ethoxylates with alkyl or arylalkyl of 12 to21 carbon atoms and 2 to 9 moles ethylene oxide adducted, and mixturesthereof.
 13. A composition according to claim 1 wherein the amount ofadditional solvent is not in excess of 50% by weight.
 14. A compositionaccording to claim 13 wherein the amount of additional solvent is in therange of from 0.4 to 40% by weight.
 15. A composition according to claim1 wherein the lipophilic carrier is selected from the group consistingof petroleum fractions, vegetable oils, synthetic triglycerides, alkylesters of fatty acids, fatty alcohols, guerbet alcohols or any mixturethereof.
 16. A composition according to claim 15 wherein the lipophiliccarrier is selected from the group consisting of aliphatic paraffiniclight distillates or vegetable oils and their derivatives.
 17. Acomposition according to claim 1 wherein the amount of lipophiliccarrier is not in excess of 95% by weight.
 18. A composition accordingto claim 1 further comprising one or more pesticides which arecompatible with the lipophilic nature of the herbicide composition. 19.A composition according to claim 18 wherein the pesticides are selectedfrom the group consisting of herbicides, fungicides, insecticides andmixtures thereof.
 20. A composition according to claim 18 wherein thepesticide is 2,4-D.
 21. A composition according to claim 1 furthercomprising other available adjuvant components.
 22. A compositionaccording to claim 21 wherein the other available adjuvant componentsare selected from the group consisting of plant nutrients, spray driftretardants, stickers, viscosity modifiers, spreaders and mixturesthereof.
 23. A concentrated essentially non-aqueous homogeneous liquidherbicide composition comprising: (a) a lipophilic solvent solublecomplex comprising the reaction product of: (i) not in excess of about35% by weight of one or more lipophobic herbicides having an acidicmoiety; and (ii) not in excess of about 99% by weight of one or moretertiary dimethylamines of the structure (CH₃)₂N—R wherein R contains analkyl group of at least 8 carbon atoms and may contain other chemicalmoieties and wherein there is at least one mole equivalent of such amineto each mole of lipophobic herbicide; and (b) not in excess of about 60%by weight of one or more essentially non-aqueous polar solvents havinglow volatility.
 24. A concentrated composition according to claim 23further comprising not in excess of 90% by weight of one or moreessentially additional solvents selected from the group consisting oflow to medium HLB surfactants.
 25. A method for improving rainfastnessof a lipophobic herbicide comprising the step of formulating thelipophobic herbicide in an essentially non-aqueous compositioncomprising: (a) a lipophilic solvent soluble complex comprising thereaction product of: (i) not in excess of about 35% by weight of one ormore lipophobic herbicides having an acidic moiety; and (ii) not inexcess of about 99% by weight of one or more tertiary dimethylamines ofthe structure (CH₃)₂N—R wherein R contains an alkyl group of at least 8carbon atoms and may contain other chemical moieties and wherein thereis at least one mole equivalent of such amine to each mole of lipophobicherbicide; (b) not in excess of about 60% by weight of one or moreessentially non-aqueous polar solvents having low volatility; (c) not inexcess of about 90% by weight of one or more additional solventsselected from the group consisting of low to medium HLB surfactants; and(d) not in excess of about 99% by weight of one or more lipophiliccarriers.
 26. A method for treating weeds comprising the step ofapplying to the weeds an essentially non-aqueous sprayable herbicidecomposition comprising: (a) a lipophilic solvent soluble complexcomprising the reaction product of: (i) not in excess of about 35% byweight of one or more lipophobic herbicides having an acidic moiety; and(ii) not in excess of about 99% by weight of one or more tertiarydimethylamines of the structure (CH₃)₂N—R wherein R contains an alkylgroup of at least 8 carbon atoms and may contain other chemical moietiesand wherein there is at least one mole equivalent of such amine to eachmole of lipophobic herbicide; (b) not in excess of about 60% by weightof one or more essentially non-aqueous polar solvents having lowvolatility; (c) not in excess of about 90% by weight of one or moreadditional solvents selected from the group consisting of low to mediumHLB surfactants; and (d) not in excess of about 99% by weight of one ormore lipophilic carriers.
 27. A method for preparing an essentiallynon-aqueous sprayable herbicide composition comprising the steps of (a)combining the following reagents: (i) not in excess of about 35% byweight of one or more lipophobic herbicides having an acidic moiety; and(ii) not in excess of about 99% by weight of one or more tertiarydimethylamines of the structure (CH₃)₂N—R wherein R contains an alkylgroup of at least 8 carbon atoms and may contain other chemical moietiesand wherein there is at least one mole equivalent of such amine to eachmole of lipophobic herbicide; and (iii) not in excess of about 60% byweight of one or more essentially non-aqueous polar solvents having lowvolatility; and (b) combining the mixture formed in (a) with not inexcess of about 90% by weight one or more additional solvents selectedfrom the group consisting of low to medium HLB surfactants and not inexcess of about 99% by weight one or more lipophilic carriers.
 28. Themethod according to claim 27 wherein the reagents in step (a) arecombined with heating and/or stirring.
 29. The method according to claim27 wherein the combining in step (b) comprises stirring the mixturewhilst warm.
 30. An essentially non-aqueous homogeneous liquid herbicidecomposition comprising: (a) a lipophilic solvent soluble complexcomprising the reaction product of: (i) not in excess of about 35% byweight of one or more lipophobic herbicides having an acidic moiety; and(ii) not in excess of about 99% by weight of one or more tertiarydimethylamines of the structure (CH₃)₂N—R wherein R contains an alkylgroup of at least 8 carbon atoms and may contain other chemical moietiesand wherein there is at least one mole equivalent of such amine to eachmole of lipophobic herbicide; and (b) not in excess of about 60% byweight of one or more essentially non-aqueous polar solvents whichassist the formation of the lipophilic solvent soluble complex, whereinthe complex is formed in the presence of the essentially non-aqueouspolar solvent but the essentially non-aqueous polar solvent may beremoved after formation of the complex if desired.
 31. An essentiallynon-aqueous homogeneous liquid herbicide composition comprising: (a) alipophilic solvent soluble complex comprising the reaction product of:(i) not in excess of about 35% by weight of one or more lipophobicherbicides having an acidic moiety; and (ii) not in excess of about 99%by weight of one or more tertiary dimethylamines of the structure(CH₃)₂N—R wherein R contains an alkyl group of at least 8 carbon atomsand may contain other chemical moieties and wherein there is at leastone mole equivalent of such amine to each mole of lipophobic herbicide;(b) not in excess of about 90% by weight of one or more additionalsolvents selected from the group consisting of low to medium HLBsurfactants; and (c) not in excess of about 99% by weight of one or morelipophilic carriers.
 32. An essentially non-aqueous homogeneous liquidherbicide composition comprising: (a) a lipophilic solvent solublecomplex comprising the reaction product of: (i) not in excess of about35% by weight of one or more lipophobic herbicides having an acidicmoiety; and (ii) not in excess of about 99% by weight of one or moretertiary dimethylamines of the structure (CH₃)₂N—R wherein R contains analkyl group of at least 8 carbon atoms and may contain other chemicalmoieties, wherein there is less than one mole equivalent of such amineto each mole of lipophobic herbicide; (iii) not in excess of about 20%by weight of one or more hydrophilic amines; wherein the total moleequivalents of the amines in (ii) and (iii) is at least equivalent tothe moles of lipophobic herbicide; (b) not in excess of about 60% byweight of one or more essentially non-aqueous polar solvents; (c) not inexcess of about 90% by weight of one or more additional solventsselected from the group consisting of low to medium HLB surfactants; and(d) not in excess of about 99% by weight of one or more lipophiliccarriers.
 33. An essentially non-aqueous homogeneous liquid herbicidecomposition comprising: (a) a lipophilic solvent soluble complexcomprising the reaction product of: (i) not in excess of about 25% byweight of glyphosate; and (ii) not in excess of about 99% by weight ofone or more tertiary dimethylamines of the structure (CH₃)₂N—R wherein Rcontains an alkyl group of at least 8 carbon atoms and may contain otherchemical moieties and wherein there is at least one mole equivalent ofsuch amine to each mole of lipophobic herbicide; (b) not in excess ofabout 60% by weight of one or more essentially non-aqueous polarsolvents selected from 1 ,3-butanediol, hexylene glycol and mixturesthereof; (c) not in excess of about 90% by weight of one or moreadditional solvents selected from the group consisting of low to mediumHLB surfactants; and (d) not in excess of about 99% by weight of one ormore lipophilic carriers selected from the group consisting of aliphaticparaffinic light distillates or vegetable oils and their derivatives.